Azo pigments of the phthalocyanine series



. metallized compounds, both in substance and on the fiber.

, fastness. provide methods of preparation of these pigments.

' phthalocyanine,

Patented Nov. 28, 1944 2,363,905 v azo PIGMENTS or run PHTHALOC sumsseams James wllllamilibby, 1h, Loukville, K1, and

Harold Edward Woodward Penna Grove, N. 1.,

assignors to E.-I. du Pont de Nen olu-s a Company, Wilmington, DeL, acorporation of llelaware No Drawing. Application January a, 194:,

Serial No. 411,130

12 Claims. (01. 8-42 This invention relates to azo-pigments of thephthalocyanine series. invention is concerned with the preparation ofderivatives of 'phthalocyanine azo It is an object of this invention toprovide new colors of the azo-phthalocyanine class, characterized byvaluable shades and excellent light Another object ofthis invention isto Still another object is to provide a method for producing dyeings oncellulose fibers which are fast to both light and washing. Other andfurther important objects of this invention will appear as thedescription proceeds.

In copending application of N. H. Haddock, Serial No. 451,076 (PatentNo. 2,351,119) waterinsoluble azo pigments of the phthalocyanine Moreparticularly, this in a position adjacent to. a hydroxygroup, or anenollzable keto group, or a group which together thol, Z-naphthbl,p-cresol, any of the various arylamides of 2,3-bydroxr-naphthoic acid,the pyrazolones, the aceto-acet-arylides, the hydroxy-quinolines, etc.

A preferred embodiment of .the invention involves the use of sui'ficientnitrite to azotize all of the available amino groups of thepolyaminophthalo'cyanine employed; but satisfactory dyeings, with forexample tetra-amino-phtha1ocy-' anine, may be obtained also by usingless than four moles of nitrous acid for every mole of tetraseries aredescribed, which are formed by azotizac; phthalocyanine with sufllcientnitrite to azotize 'ing various amino-phthalocyanines andcoupling,

" ing matters of the same class are produced on the fiber, byimpregnating cellulosic fiber with a solution of an azotizedamino-phthalocyanine, followed by coupling on the fiber, that is,developing with an azo coupling component devoid of water-solubilizil'iggroups, such as carboxy and sulionic acid. The washing fastness of thedyeings so produced is excellent. ,The light fastness of these pigments,produced both in substance In copending apamino-phthalocyanine. As anexample, a satis- Jactory dyeing suitable for metallization may "beobtained by azotizing tetra-amino-copperin mind that the polydiazoniumphthalocyanines are not particularly stable, and even where sufilcientnitrite is used to azotize all of the amino groups, decomposition ofsome of the diazo groups may take place prior to complete coupling;thus,

"in the case of tetra-amino-copper-pht halocyanine, for instance, theactual dyeing on the fiber may under circumstances be a mixture of andon the fiber, varies from fair to good, dependwhen our invention isapplied to the develop-' ing upon the coupling components involved.

tions, and are then treated with aqueous solutions of compounds ofmetals capable of forming me-- talllc complexes with ortho-hydroxy-azodyes," new metal complex azo pigments of the phthalocyanlne series areformed, whichare in general faster to light than the unmetallizedpigments.

Any of the amino-phthalocyanines mentioned iupopending applicationSerialNo. 444,107 (Patent No. 2,339,740) may be used as the-diazo comingprocedures may be employed. More particuthe tetrakisaz'o, trisazo,disazo and even monoazo derivatives of the phthalocyanine compound.

ment of color on the fiber. both dyeing and printlarly,'any one of thefollowing methods may be used:

40 '1. The fiber may be impregnated with a soluponent in the preparationof the pigments or dyeings which are to be metallized. For example: The(3) and (4) di-, triand tetra-amino derivatives of metal-freephthalocyanine, copper cobaltphthaloeyanine, and nickeLphthalocyanineare useful for the purposes of this invention. The couplingcomponentssuittion of the azotized polyamino-phthalocyanino and then treated withan alkaline solution of the appropriate coupling component.

2. The fiber may be prepadded with a solution of a cellulose substantivecoupling component, as

I for example, an arylamide of 2,3-rhydroxy-naphthoic acid and thentreated with a solution of an azotized polyamino-phthalocyanine, 1 thepH of which has been raised above Congo Red neutrality with sodiumacetate.

3. The fiber may be printed with a solution of an azotizedpolyamino-phthalocyanine which has been thickened with anordinary-printing paste thickener, such as gum tragacanth; said printingable for use are those in which coupling occurs 3 y th be in an aque usalkaline As examples of satisfactory coupling- 'C. for one hour.

' fastness is obtained.

'azotized amino-phthalocyanine for the purpose of impregnating cellulosefiber, there may be employed solutions prepared by dissolving in waterphthalccyanine diazcnium compounds which have been stabilized in dryform by conversion to the inorganic double salts, isodiazotates, etc.-See, for instance, copending application of N. H. Haddock,

. Serial NO. 443,668 (Patent No. 2,349,090).

The metallizing agents suitable for use with the present inventioninclude water-soluble compound of metals capable of forming complexcompounds; for example, the water-soluble'salts of copper, cobalt,nickel and chromium, or more generally, metals of atomic Weights between51 and 64.. As practical examples of such water=soluble Example II Fiveparts of cotton piece-goods were impregnated with the solution ofazot'ized tetra-(4) amino-copper-phthaloe-cyanine in the same manner asin Example I. The piece so impregnated was then aftertreated in a bathconsisting of o parts of water, 0.2 part of B-hydroxy-quinoline, 1 partof 2-normal sodium hydroxide, and 1 part of 2-normal sodiumcarbonateat/room tempera- 3 ture for a period of 15 minutes.

The dyed fabric was then aftertreated for 15 minutes at the boil in a,bath consisting of 200 parts of water, 0.25 parts of copper acetate, andsumcient ammonia to redissolve the copper hydroxide at firstprecipitated by the addition of ammonia. The dyeing obtained was a dullgray shade with excellent washing iastness and excellent light'fastness.Dyeings of similar shade with excellent light and washing fastness areobtained if the copper acetate plus ammonia used in the aboveaftertreating bath is replaced by an amount salts may be mentionedcopper acetate, copper V sulfate, cuprammonium sulfate, copper chloride,

nickel acetate, cobalt acetate, cobalt chloride,

chromium acetate and chromium fluoride.

The dyeings are aitertreated in aqueous baths containing one or more ofthe said metallic agents for from about 10 to about 60 minutes at ternperatures which may range from about room tem= perature to about theboiling point of the bath. The volume of the aitertreating bath is notpar ticularly critical, but sumcient volume should be employed so thatthe dyeing is completelycow cred for essentially the major portion ofthe aftertrea'ting procedure. The amount of the metallizing agent usedmay be varied within reasonable limits, but there is normally employed aweight equivalent to from about,1% to about 10% of the weight of thefabric being aftertreated. The pH of the bath should not be reducedbelow the value obtainable by merely dissolving themetallic salt inneutral water.

The following examples are given to illustrate the invention but withoutintent to limit it in any way. Parts are by weight of 100%mate1ialexcent where otherwise specified.

tetra-(e)-amino-phthalocyanine were added 8.3

parts of Iii-normal hydrochloric acid, and sufiicientice to reduce thetemperature to approximately 5 (Z2. Then 1 part of 2-normal sodiumnitrite was added and the resulting solution stirred for one hour at 05C. At the end of that time, the solution was filtered and diluted to 175parts with water. Five parts of cotton piecegoods were turned in thissolution, held at 05 The piece was then removed, rinsed in cold waterand aftertreated in a bath consisting of 250 parts of water, 0.2 part of-2- naphthol, 1 part of Z-normal sodium hydroxide .ings of similar shadeand similarly excellent solution and 1 part of 2-normalsodium carbonatecopper acetate. The dyeing obtained was a chocolate-brown shade and hadexcellent washing fastness and light fastness. I

If, in place of the copper acetate used in the above aftertreating bath,nickel acetate, cobalt acetate or chromium acetate is used, 9, dyeing ofsimilar shade with excellent washing and light of nickel acetate, cobaltacetate or chromium acetate equivalent to the copper acetate.

\ v Example III Tetra- (a -amino-copper 'phthalocyanine was azotized andused to dye five parts of cotton piecegoods in a manner similar to thatdescribed in Example I. The dyeing was then aftertreated for 15 minutesat5-1(l C. in a bath consisting of 250 parts of water, 0.4 part ofaceto-acet-p-phenetidide, 1 part of Z-normal sodium hydroxide and 1 partof Z-normal sodium carbonate. The green dyeing resulting had excellentwashing fastness and good light fastness. One-half of this dyeing wasthen treated in an aftertreating bath con-. talning copper acetate asdescribed in Example I. The dyeing, a dull green shade, had excellentwashing "fastness and light fastness. I

If in place, of the copper acetate of the above-- mentioned bath nickelacetate, cobalt acetate or chromium acetate is used in equal weight,dyewasbing and light fastness are obtained In the following table arelisted shades of other dyeings made from azotized amino phthalocyanineand azo coupling components devoid of water-solubiliaing groups such ascarboxy and onic acids, the dyeings being made in manners analogous tothose described in the preceding examples. 'The amino phthalocyaninesused in these cases, as well as the coupling components andafter-metallizing baths employed,.are listed.

v'llhe'shades are indicated. The washing fastness in all cases isexcellent, and the light fastness ranges from very good to excellent.

Azotized telglgalminocopper-p a ocya- Ex. treated on the Then treatedwith Shade fiber with IV pars-Clesol Copper acetate Dull green. V ..dNickelacetate" reen. VI "do-.- Cobalt acetate. Do. VII do Chromiumacetate Do. VIII l-phenyl-3-methyl-5- Copper acetate Dull green.

pyrazolone.

do Nickel acetate Drab green.

Cobalt acetate Do. do Chromium acetate D0. 8-hydroxy-quinoline Copperacetate Green gray. XIII... pars-Cresol .do Dull green gray.

Example XIV To a slurry of 159 parts of tetra-(4) -aminocopperphthalocyanine in 1500 parts of water a was iced to C. and

. ascaooo I there were added 1000 parts of concentrated bydrochloricacid. After stirring 1 hour, the slurry 69 parts of sodium nitrite wereadded. After stirring about 15 minutes-at C. the green solution 'wasfiltered. It was run into a solution of 1'70 parts of2,4-dihydronquinoline and 42 parts of-sodium hydroxide and 106 parts ofsodium carbonate in 3000 parts of water. While the 'solution of thediazonium compound was entering the solution of dihydroxy quinoline, icewas added to keep the temperature at C. and 260 parts of sodiumhydroxide were added to keep the solution slightly alkaline to BrilliantYellow paper. The pigment was filtered and washed, then slurried inabout 3000 parts of water. A solution comprising 400 parts of ammoniumhydroxide (sp. gr. 0.8) and 550 parts of molar copper sulfate was thenadded and the mixture was heated at 90 C. for 3 hours.- The pigment wasfiltered and washed.

A dried portion of this pigment was milled in lithographic varnish, andthe dark green ink obtained was found to possess excellent lightfastness inmasstone and undertone. A zinc oxide tint of this ink had astrong, dull green shade and good light fastness.

A portion of this pigment was of which contained a pigment bindingagent, and the emulsion was printed on cotton and baked at 150 C. for 5minutes. A dark green print was obtained which was fast to soa'pingcellent light fastness.'

nickel compound had better fastness to light when used to tint a zincoxide ink.

, Example XVI When 152 parts of a-hydroxy-quinoline were and had exilsed' in place of 170 pafts of 2,4-dihydroxyquinoline in Examples XIVand XV, igments were obtained which gave gray inks and textile droxidesolution may be replaced by 272 parts or sodium acetate crystals. Ifacetates of the metals are used instead of chlorides or sulfates, themetallization may be carried out without the addition of ammoniumhydroxide or sodium acetate. Other details in the above examples, suchas concentration, temperature and time in the diazotization, couplingand metallization may be varied within reasonable limits withoutaffecting the results obtained.

In the claims below, the expression azoic coupling component shall beunderstood as referred to coupling components which are free ofwatersolubilizing groups (such as sulfonic or carb'oxylic) as typifiedby the naphthols, the cresols,

'the arylamidesof '2,3-hydroxy naph'thoic acid,

, incorporated in a water-in-lacquer emulsion, the lacquer phase thenon-sulfonated aryl-methyl-pyrazolones, the aceto-acetarylides, and thehydroxy-quinolines.

y We claim: 7

' 1. A metal complex form of an azo coloring compound of the generalformula I greater than 4, the metal in said metal complex prints of goodlightfastness. These grays were 7 morenearly neutral than thegreenish-gray of the unmetalhzed pigment.

' Example XVII A solution of the diazonium compound was prepared as inExample XIV. Tonthis was added a solution of- 180 parts of1-phenyl-3-methyl-5- pyrazolone in 500 parts of water and 44 parts ofhydrochloric acid Then 136 parts of sodium acetate crystals were addedand enough sodium hydroxide about 260 parts) to make the solutionneutral to Congo red. The pi ment was filtered, then treated with copperammonium sulfate as in Example XIV. The pigment gave s mple xvm darkgreen inks and textile prints of very good fastness to light.

place of,170 parts of 2,4-dihydroxy-quinoline in Examples XIV and 1V.Pigments were obtained which gave strong, gray inks and textile "printsof good light'fastness.

It will be understood that the above examples are merely illustrativeandth'at the details may be varied liberally within the skill of thosee'n- 'gagedinthishart. Thus,inExamplesXIVto xvlllinclusiv'e, the 400parts of ammonium hyform being a member of the group consisting ofcopper, nickel, cobalt and chromium and being present in addition to anymetal atoms which radical. 2. A metal complex form of an azo coloringcompound of the general formula wherein CuPc designates the radical ofcopper phthalocyanine, Q is the radical of an azoic coupling component,while a: is a number not greater than 4', the metal in said metalcomplex form being a member of the group consisting of copper, nickel,cobalt and chromium and being present in addition to the copper atom inthe CuPc radical above defined.

3. Textile fiber being colored with a metal complex form of anazo-pigment of the phthalocy anine series as defined in claim 1.

4. Cellulosic textile fiber having developed on the fiber a metalcomplex form of a copperphthalocyanine and compound as defined in claim2. v i

- 5. The process of producing novel coloring matters of thephthalocyanine series, which comprises reacting with a water-solublecompound of a metal whose atomic weight is between 51 and 64 upon an azocompound of the phthalocyanine series obtained by coupling an azotizedpoly amino-phthalocyanine to an azoic coupling component. j I

6. The process of producing novel coloring matters of thephthalocyanineseries, which comprises reacting with a water-soluble saltof a metal-from the group consisting of copper, nickel,

cobaitind chromium upon an aao compound obtained by coupling an aaotized'tetra-amino coppa-phthalocyanine to an aaoic coupling com 'I. Theprocess of coloring textile fiber, which comprises developing on thefiber an azo dye by coupling on the ilber an aaotizedpolyaminophthaloeyanine to an azoic coupling component,

andthen treating the dyed fiber with a water.- aoluble compound ofametal whose atomic weight may be present as part of the phthalocyanineponent, and then treating the dyed fiber with a water-soluble salt of ametal selected from the group consisting of copper, nickel, cobalt andchromium to metalllze the azo dye on the fiber.

9. ,The process of dyeing celluloslc textile material, which comprisesimpregnating the material with a. solution of azotizedcopper-tetra-amino phthalocyanine, then treating the impregnatedmaterial with a developing bath containing an azoic coupling component,to produce an azo dye on the fiber, and finally treating the dyedmaterial with an aqueous solution of a, salt of a metal selected fromthe group consisting of copper, nickel, cobalt and chromium to metallizethe azo dye on the fiber.

10. The nickel complex of a r ,azo dye obtained by coupling an azotizedtetraamlnwcopper-phthalocyanine to. ivdroxyquinollne.

11'. Textile material colored with e metallized ezo-phthalocyanine dyeobtained by padding the textile material with an azotizedpolyaminophthalocyanine, developing on; the fiber with 8-hydroxy-quinoline and metallizing the azo dye on the fiber by treatmentwith an aqueous solution of a water-soluble compound of copper.

12. Textile material colored with a metalllzed azo-phthalocyanine dyeobtained by padgthe textile material with an azotizedpolyamlnophthalocyanine, developing on the fiber with 2- naphthol andmetallizing the azo dye on the fiber by treatment with an aqueoussolution of a we.- ter-soluble compound of copper.

